U.S. patent number 4,584,245 [Application Number 06/499,790] was granted by the patent office on 1986-04-22 for laminated safety glass.
This patent grant is currently assigned to Asahi Glass Company Ltd.. Invention is credited to Takeshi Harada, Kazuhiko Kuga, Kohji Kurita, Hiroshi Washita, Hiroyuki Watanabe.
United States Patent |
4,584,245 |
Kuga , et al. |
April 22, 1986 |
Laminated safety glass
Abstract
Transparent or translucent laminated safety glass having an at
least two layered structure comprising a synthetic resin layer
having an exposed surface and a hard substrate layer wherein the
exposed surface of the synthetic resin layer has a cross-linked
structure of cross-linkable groups introduced and cross-linked in
said surface.
Inventors: |
Kuga; Kazuhiko (Yokohama,
JP), Washita; Hiroshi (Yokohama, JP),
Watanabe; Hiroyuki (Yokohama, JP), Kurita; Kohji
(Yokohama, JP), Harada; Takeshi (Yokohama,
JP) |
Assignee: |
Asahi Glass Company Ltd.
(Tokyo, JP)
|
Family
ID: |
27468492 |
Appl.
No.: |
06/499,790 |
Filed: |
May 31, 1983 |
Foreign Application Priority Data
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Jun 8, 1982 [JP] |
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57-96952 |
Jun 8, 1982 [JP] |
|
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57-96953 |
Jun 25, 1982 [JP] |
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57-108473 |
Aug 27, 1982 [JP] |
|
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57-147830 |
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Current U.S.
Class: |
428/409; 428/420;
428/423.3; 428/425.6; 428/426; 428/447 |
Current CPC
Class: |
B32B
17/10018 (20130101); B32B 17/10174 (20130101); B32B
17/10697 (20130101); B32B 17/1077 (20130101); B32B
17/10853 (20130101); C08G 18/0823 (20130101); B32B
17/10862 (20130101); Y10T 428/31 (20150115); Y10T
428/31663 (20150401); Y10T 428/31601 (20150401); Y10T
428/31554 (20150401); Y10T 428/31536 (20150401) |
Current International
Class: |
B32B
17/10 (20060101); B32B 17/06 (20060101); C08G
18/08 (20060101); C08G 18/00 (20060101); B32B
027/40 (); B32B 007/02 () |
Field of
Search: |
;428/423.3,425.6,409,447,426,420 ;427/302 ;156/331.1 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0122355 |
|
Sep 1979 |
|
JP |
|
1576394 |
|
Oct 1980 |
|
GB |
|
Primary Examiner: Robinson; Ellis P.
Attorney, Agent or Firm: Oblon, Fisher, Spivak, McClelland
& Maier
Claims
We claim:
1. A transparent or translucent laminated safety glass having an at
least two layered structure, comprising:
a polyurethane thermoplastic resin layer deposited on a hard
substance, the exposed surface of said polyurethane resin layer
having a cross-linked structure which is formed by the light or
moisture initiated cross-linking of cross-linkable functional
groups, the resin of said exposed surface containing carboxylic
acid groups.
2. The laminated safety glass of claim 1, wherein the
cross-linkable functional groups are introduced into the exposed
surface of said thermoplastic resin layer by reacting the
carboxylic acid groups which are within the polyurethane resin on
the exposed surface of said layer with a compound which contains
cross-linkable groups and epoxy groups.
3. The laminated safety glass of claim 2, wherein the
cross-linkable functional groups in said compound which reacts with
the carboxylic acid groups in said polyurethane resin are initiated
in their cross-linking reaction by light or moisture.
4. The laminated safety glass of claim 3, wherein said compound
containing epoxy groups and light initiated, cross-linkable
functional groups is at least one compound selected from the group
consisting of glycidoxy cinnamate, glycidoxy acrylate and glycidoxy
methacrylate.
5. The laminated safety glass of claim 3, wherein said compound
containing epoxy groups and moisture initiated, cross-linkable
functional groups is glycidoxy alkyltrialkoxysilane.
6. The laminated safety glass of claim 1, wherein said hard
substrate is a layer of inorganic glass.
7. The laminated safety glass of claim 1, wherein said hard
substrate is a laminate of a pair of inorganic glass sheets having
an intermediate film interposed between the two glass sheets.
8. A transparent or translucent laminated safety glass having an at
least two layered structure, comprising:
a polyurethane thermoplastic resin layer deposited on a hard
substrate, the exposed surface of said polyurethane resin layer
having a cross-linked structure which is formed by the light
initiated cross-linking of cross-linkable functional groups
selected from the group consisting of cinnamic acid groups, acrylic
acid groups, methacrylic acid groups and combinations thereof.
9. The laminated safety glass of claim 2, wherein said hard
substrate is a layer of inorganic glass.
10. The laminated safety glass of claim 2, wherein said hard
substrate is a laminate of a pair of inorganic glass sheets having
an intermediate film interposed between the two glass sheets.
11. A transparent or translucent laminated safety glass having an
at least two layered structure, comprising:
a polyurethane thermoplastic resin layer deposited on a hard
substrate, the exposed surface of said polyurethane resin layer
having a cross-linked structure which is formed by the moisture
initiated cross-linking of cross-linkable alkoxysilyl functional
groups.
12. The laminated safety glass of claim 11, wherein said hard
substrate is a layer of inorganic glass.
13. The laminated safety glass of claim 11, wherein said hard
substrate is a laminate of a pair of inorganic glass sheets having
an intermediate film interposed between the two glass sheets.
Description
The present invention relates to laminated safety glass having an
at least two layered structure comprising a synthetic resin layer
having an exposed surface and a hard substrate layer. More
particularly, the present invention relates to laminated safety
glass comprising a synthetic resin layer having an exposed surface
having improved surface properties.
A laminated sheet composed of a glass sheet and a synthetic resin
sheet is well-known as laminated safety glass. For instance, a
laminated sheet having a three-layered structure of glass-polyvinyl
butyral glass is widely used as safety glass for automobiles. The
synthetic resin layer interposed between the glass sheets is
referred to as an intermediate film, and for this purpose, various
synthetic resins such as polyvinyl butyral, polyurethane and the
like are used or proposed to be used. On the other hand, among
various types of laminated safety glass composed of glass and a
synthetic resin, a laminated sheet with its synthetic resin layer
exposed, e.g. a laminated sheet having glass on one side and a
synthetic resin on the other side, such as glass-synthetic resin or
glass-synthetic resin-glass-synthetic resin, has become attractive
as a prospective material for safety glass for automobiles. This
laminated safety glass is believed to be safer than the
conventional laminated safety glass with both sides made of glass.
For instance, if this laminated safety glass is used as front glass
of an automobile with its synthetic resin surface facing inside,
the synthetic resin surface is believed to protect an occupant such
as a driver from being injured when he hits the front glass and
even when the glass is shattered, the synthetic resin layer is
believed to prevent or minimize the scattering of the glass
fragments into the inside of the automobile. Such a laminated
safety glass having a glass surface on one side and a synthetic
resin surface on the other side will be hereinafter referred to as
"resin-laminated glass".
The resin-laminated glass is disclosed, for instance, U.S. Pat.
Nos. 3,881,043, 3,806,387, 3,979,548 and 3,808,077, U.K. Pat. Nos.
1,401,986 and 1,576,394 and German Pat. No. 2,240,580. As disclosed
in these prior art references, the synthetic resin layer is usually
made of polyurethane. Further, it is well known to use polyurethane
as an intermediate film in two-ply glass. The polyurethane includes
so-called thermoplastic polyurethane and thermosetting
polyurethane. The thermoplastic polyurethane is a linear polymer
and is usually prepared by reacting a diol having a high molecular
weight, a chain extender and a diisocyanate compound, whereas the
thermosetting polyurethane is a cross-linked polymer and is
prepared, for instance, by reacting a diol having a high molecular
weight, a cross-linking agent and a diisocyanate compound. The
synthetic resin layer is required to be firmly bonded to glass.
When a thermosetting polyurethane is used as the synthetic resin
layer, however, there is a problem that the thermosetting
polyurethane can not firmly be bonded to glass. On the other hand,
the thermoplastic polyurethane is capable of being firmly bonded to
glass, but so long as it is used as a synthetic resin layer in the
resin-laminated glass, the other surface is exposed and the exposed
surface has certain problems in its properties. Namely, the
thermoplastic polyurethane does not have adequate weather
resistance and is susceptible to an influence of a solvent. These
problems are discussed in detail in U.K. Pat. No. 1,576,394.
The U.K. Patent discloses an invention whereby the abovementioned
problems are solved by providing a synthetic resin layer comprising
two polyurethane layers, namely the surface layer is made of a
thermosetting polyurethane and the layer bonded to glass is made of
a thermoplastic polyurethane. These two types of polyurethanes are
capable of being firmly bonded to each other. Accordingly, by this
invention, it is possible to solve both problems relating to the
bonding of the synthetic resin layer to glass and the surface
properties. However, this invention does not necessarily solve all
the problems. Firstly, in this invention, it is necessary to
prepare a sheet (which is referred to as a pre-formed polymeric
sheet) comprising two different polyurethanes, thus requiring
relatively complicated process steps. For instance, as described in
the U.K. Patent, it is required to employ a method wherein a
mixture of liquid monomers for one polyurethane is cast on a sheet
of the other polyurethane to form unitary structure of a method in
which one polyurethane is dissolved in a solvent and the solution
thereby obtained is coated on the surface of the other
polyurethane. The second problem resides in that the thermosetting
polyurethane loses plasticity once it is hardened. First of all,
there is a restriction in the process for forming a sheet or film
of the thermosetting polyurethane (the casting method for hardening
is usually the only process), and extrusion molding, press-molding
or other methods suitable for forming can not usually be employed.
Accordingly, it is difficult to obtain a smooth sheet or film
having a uniform thickness. Further, in the case where the material
has plasticity, it is usually possible to form a flat smooth
surface by pressing it with a press having a flat surface, but in
the case of the thermosetting polyurethane, it is impossible to
form such a flat surface once the plasticity has been lost.
Likewise, for this reason, the thermosetting polyurethane does not
have adequate adhesiveness. Thirdly, the thermosetting polyurethane
is inferior to the thermoplastic polyurethane in the physical
properties required for the resin-laminated glass, such as
penetration resistance or impact resistance.
In the above-mentioned prior art references, such various problems
are not yet solved. Apart from the question of the surface
properties, a thermoplastic resin, particularly a polyurethane
thermoplastic resin, is believed to be most suitable for use as the
synthetic resin layer for the resin-laminated glass. However, it is
not necessarily required to form the entire synthetic resin layer
with a thermoplastic resin, and a thermosetting resin may be used
e.g. for bonding the layers in a multi-layered structure of a
synthetic resin layer or for bonding a synthetic resin layer to a
hard substrate where the hard substrate is made of organic glass.
Even in such a case, the thermosetting resin layer to be present
should preferably be thin and the major portion of the synthetic
resin layer, especially the major portion including the surface
layer constituting the exposed surface, should preferably be made
of a thermoplastic resin. Such a thermoplastic resin layer having a
single or multi-layered structure which may include a thermosetting
resin layer, will be hereinafter referred to simply as a synthetic
resin layer.
The present inventors have found that in the above-mentioned
laminated safety glass having an at least two layered structure
comprising a synthetic resin layer and a hard substrate layer such
as a glass sheet, it is possible to obtain superior surface
properties by providing a cross-linked structure of cross-linkable
functional groups in the exposed surface of the synthetic resin
layer.
Thus, the present invention provides transparent or translucent
laminated safety glass having an at least two layered structure
comprising a synthetic resin layer having an exposed surface and a
hard substrate layer, wherein the exposed surface of the synthetic
resin layer has a cross-linked structure of cross-linkable groups
introduced and cross-linked in said surface.
Now, the present invention will be described in detail with
reference to the preferred embodiments.
In the accompanying drawings, FIGS. 1 to 4 are cross sectional
views illustrating various embodiments of the laminated safety
glass of the present invention.
FIG. 1 illustrates a two layered structure comprising a synthetic
resin layer and a hard substrate.
FIG. 2 illustrates a three layered structure comprising two
synthetic resin layers and a hard substrate.
FIG. 3 illustrates a four layered structure comprising three
synthetic resin layers and a hard substrate.
FIG. 4 illustrates a five layered structure comprising two
synthetic resin layers and a hard substrate having a three layered
structure.
FIGS. 5 to 8 are cross-sectional views illustrating the processes
for the preparation of various laminated structures for the
laminated safety glass of the present invention.
FIG. 5 illustrates the preparation of a two layered structure
comprising a synthetic resin layer and a hard substrate.
FIG. 6 illustrates the preparation of a three layered structure
comprising two synthetic resin layers and a hard substrate.
FIG. 7 illustrates the preparation of a three layered structure
comprising two synthetic resin layers and a hard substrate.
FIG. 8 illustrates the preparation of a four layered structure
comprising a synthetic resin layer and a hard substrate having a
three layered structure.
The cross-linkable functional groups (hereinafter referred to
simply as "cross-linkable groups") are introduced into a synthetic
resin surface which constitutes or will constitute the exposed
surface of the synthetic resin layer. The timing of the
introduction may be after the laminated safety glass has been
assembled or at any optional stage prior to the assembling. The
introduction into a surface is meant for introducing the
cross-linking groups into an exposed surface of the synthetic resin
or into a surface which has been preformed to constitute an exposed
surface of the synthetic resin. The surface into which the
cross-linking groups have been introduced, may be subjected to a
further processing or modification including a secondary processing
such as surface smoothing treatment during the heat pressing
operation which will be described hereinafter. However, if the
synthetic resin contains cross-linkable groups prior to the
fabrication into a sheet or film (in such a case, the
cross-linkable groups are usually distributed throughout the entire
synthetic resin layer), such cross-linkable groups are not regarded
as the cross-linkable groups introduced into a surface. However,
the synthetic resin layer into which the cross-linkable groups are
to be introduced, may already contain in its surface or in its
internal portion, cross-linkable groups which may be the same as or
different from the cross-linkable groups to be introduced.
The laminated safety glass of this invention has a cross-linked
structure of cross-linkable groups introduced in the exposed
surface of its synthetic resin layer. The exposed surface having
such a cross-linked structure has superior surface properties such
as weather resistance and solvent resistance. Besides, since this
cross-linked structure is located at the surface, it does not give
substantial effects to the nature of the synthetic resin other than
the surface portion. Accordingly, it is possible to select a
synthetic resin having the most suitable properties other than the
surface property. For instance, it is possible to employ a
synthetic resin such as a polyurethane thermoplastic resin which is
most suitable for a laminated safety glass apart from the surface
property.
As the cross-linkable groups, there may be used various
cross-linkable groups which are cross-linkable by heat, light,
moisture or a chemical substance. It is preferred to use functional
groups cross-linkable by the action other than heat, and
particularly preferred are functional groups cross-linkable by
light or moisture. The reason is that for the fabrication of
laminated safety glass, a heating step is required not infrequently
and if functional groups cross-linkable by heat are present, it is
likely that unnecessary cross-linking takes place during the
heating step. For instance, in many cases, laminated safety glass
is fabricated by laminating a synthetic resin sheet or film with a
hard substrate by means of heat pressing or any other heating means
for lamination. Further, in a case where a multi-layered synthetic
resin sheet or film is used, it is quite common to employ a method
involving a heating step for the preparation of such a laminated
heat or film. In such cases, it is common to preliminarily
introduce cross-linkable groups into such a synthetic resin sheet
or film and then employ the sheet or film for the preparation of
laminated safety glass or a synthetic resin laminate. If the
cross-linkable groups are highly sensitive to heat and susceptible
to cross-linking by heat, there will be a possible disadvantage
such that the cross-linking takes place during the press heating
whereby the smoothness of the surface will be impaired.
Accordingly, the cross-linkable groups are preferably functional
groups cross-linkable by the action other than heat, particularly
functional groups cross-linkable by light or moisture. However, in
a case where a finished synthetic resin surface of an already
fabricated laminated safety glass is to be treated, the
cross-linkable groups may be functional groups cross-linkable by
heat. The introduced functional groups are then cross-linked by a
suitable means to induce the cross-linking. For instance, in the
case of the functional groups cross-linkable by light, the
cross-linking is conducted by light such as ultra-violet ray, and
in the case of the functional groups cross-linkable by moisture,
the cross-linking is carried out by water in a liquid state or a
vapor state. For instance, in the introduction and cross-linking of
alkoxysilyl groups as an example of functional groups
cross-linkable by moisture, firstly the surface which constitutes
or will constitute an exposed surface of a synthetic resin layer,
is made of a synthetic resin having active groups such as
carboxylic groups, for instance, a polyurethane thermoplastic resin
containing carboxylic groups, as mentioned hereinafter, and then a
compound having a group linkable to such an active group
(hereinafter referred to as a "linkable group") and an alkoxysilyl
group as a moisture-cross-linkable group, is, by itself or in a
form of its solution, coated thereon and reacted, whereby the
alkoxysilyl group is introduced into the surface of the synthetic
resin. Then, this surface is moistened (for example, by applying
water thereto or by placing it in an air containing moisture) to
hydrolyze and convert the alkoxysilyl group to a silanol group.
This silanol group is then permitted to naturally undergo
condensation by dehydration, or positively dehydrated to form a
cross-linkage.
In FIGS. 1 to 4, various embodiments of the laminated safety glass
of the present invention are shown in their cross sections.
FIG. 1 is a cross sectional view of laminated safety glass having a
two layered structure comprising a synthetic resin layer 1 and a
hard substrate layer 2 made of e.g. inorganic glass (hereinafter
referred to simply as "glass"). The exposed surface A of the
synthetic resin layer 1 has a cross-linked structure of
cross-linkable groups introduced in the above-mentioned manner,
whereas the other surface B is bonded to the hard substrate 2. FIG.
2 is a cross sectional view of laminated safety glass wherein the
synthetic resin layer 1 has a two layered structure. For instance,
the synthetic resin layer 3 having an exposed surface A is a layer
made of a polyurethane thermoplastic resin having active groups
such as carboxylic groups, as mentioned in hereinafter whereas the
inner synthetic resin layer 4 is made of a usual polyurethane
thermoplastic resin. FIG. 3 illustrates laminated safety glass
similar to the one shown in FIG. 2, but wherein the synthetic resin
layer has a three layered structure, and between the inner
synthetic resin layer 4 as shown in FIG. 2 and the hard substrate
layer 2, there is provided a third synthetic resin layer 5 having
strong bonding force to both layers. In this case, if the hard
substrate layer 2 is made of organic glass, the third synthetic
resin layer 5 may be a layer of a thermosetting resin. FIG. 4
illustrates laminated safety glass similar to the one shown in FIG.
2, but wherein the hard substrate layer 2 has a three layered
structure, and this hard substrate is composed of two glass layers
6 and 7 and an intermediate film 8 such as a butyral film
interposed between the glass layers.
In the present invention, the hard substrate layer is made of a
sheet material having greater hardness than the synthetic resin,
such as a sheet of glass (i.e. inorganic glass) or a sheet of
polycarbonate, polymethylmethacrylate or other organic glass. The
third substrate may be of a single layered structure or a
multi-layered structure as mentioned above. In the case of the
multi-layered structure, the surface to which the synthetic resin
is bonded e.g. by heat pressing and the exposed exterior surface
are made of a hard material, but the intermediate layer interposed
between the two hard material layers may be made of a soft material
such as a butyral resin. In the case of a glass sheet, it may be
the one strengthened by e.g. air-cooling or chemical strengthening.
Further, the glass sheet may be colored or may have a thin film
such as a heat ray reflecting film. In the case of an organic glass
sheet, it may be the one subjected to certain treatment such as
stretching treatment, or it may have a thin layer such as a hard
coating layer. Further, the organic glass sheet may be colored or
may have certain printed design. Furthermore, it may have partially
a non-transparent portion. The hard substrate is preferably
transparent or translucent as a whole. It is particularly preferred
that the hard substrate has superior optical properties. The
overall thickness of the hard substrate is preferably at least 0.5
mm, more preferably from 1 to 50 mm. This hard substrate may be a
flat sheet or may have various shapes suitable for a front window
or rear window of a automobile. Further, depending upon the
particular use, it may be the one having a varied thickness, such
as a lens. A particularly preferred hard substrate is composed of a
transparent or colored transparent glass sheet having a single or
multi-layered structure.
In the present invention, the synthetic resin layer is made of a
synthetic resin which is softer than the hard substrate. This
synthetic resin is made of a transparent or translucent material.
However, sheet or film materials per se prior to lamination may be
non-transparent (for instance, because of a finely roughened
surface) so long as they are able to eventually become transparent
or translucent when laminated. The synthetic resin may be colored
or may partially have a non-transparent portion. The synthetic
resin constituting the exposed surface is preferably a
thermoplastic resin. Particularly, preferred is a polyurethane
thermoplastic resin, as mentioned hereinafter. As the synthetic
resin which does not constitute the exposed surface, there may be
used various kinds of synthetic resins. However, even when a
particular synthetic resin does not constitute the exposed surface,
if the physical properties of the overall synthetic resin layer
depend on the particular layer, namely if the particular layer is
substantially thicker than other synthetic resin layers, such a
synthetic resin should preferably be a thermoplastic resin,
particularly a polyurethane thermoplastic resin. In the case where
the synthetic resin layer has a single layered structure, a
thermoplastic resin sheet is used. In the case of the multi-layered
synthetic resin layer, the synthetic resins may be used in the form
of sheets or films. In the present invention, a sheet is meant for
a material having a thickness at least 0.2 mm, and a film is meant
for a material having a thickness of less than 0.2 mm. Accordingly,
a synthetic resin layer may be formed by using e.g. a polyurethane
thermoplastic resin film having active groups readily linkable to
the above-mentioned linkable groups and a thick polyurethane
thermoplastic resin sheet. The overall thickness of the synthetic
resin layer is not critical, but preferably is at least 0.2 mm,
more preferably from 0.4 to 10 mm.
In the present invention, the above-mentioned thermoplastic resin
is preferably a polyurethane thermoplastic resin. Other
thermoplastic resins which may be used, include a polyester resin,
a butyral resin, a polydiene resin, an ethylene-vinylacetate
copolymer, a polyolefin elastomer or other relatively soft
thermoplastic resin or thermoplastic elastomer. However, from the
viewpoints of the transparency, shock resistance, penetration
resistance or other physical properties, a polyurethane
thermoplastic resin is most preferred. The polyurethane
thermoplastic resin is a synthetic resin containing a number of
urethane groups and having thermoplasticity. This synthetic resin
may contain, in addition to urethane groups, urea groups,
allophanate groups, biuret groups or other groups formed by the
reaction of an active hydrogen-containing group with an isocyanate
group. Further, it may contain isocyanurate groups, carbodiimide
groups or other groups derived from isocyanate groups. Further, it
may of course contain ester groups, ether groups, carbonate groups
or other groups derived from the high molecular weight polyol per
se, as well as certain groups derived from compounds such as chain
extenders or cross-linking agents. In the case of polyurethane
which constitutes the exposed surface, in order to facilitate the
introduction of functional groups cross-linkable by light or
moisture, it preferably has active groups such as carboxylic acid
groups or partially amino groups, which are linkable to a compound
having such functional groups.
The polyurethane thermoplastic resin is basically a linear polymer
obtainable by reacting a high molecular weight diol, a chain
extender and a diisocyanate compound. However, it may contain a
small amount of branched chains. For instance, it may be a
substantially linear polymer having a small amount of branches
which is obtainable by using an at least tri-functional polyol,
cross-linking agent or polyisocyanate in combination with the
above-mentioned bi-functional compound. In addition to the three
major materials i.e. the high molecular weight diol, the chain
extender and the diisocyanate compound, there may be used, if
necessary, various subsidiary materials for the preparation of a
polyurethane thermoplastic resin. It is usually required to use a
catalyst as a subsidiary material. Depending upon the particular
purpose, a cross-linking agent, a coloring agent, a stabilizer, a
ultra-violet absorption agent, a flame retardant or other additives
may be used as subsidiary materials.
As the high molecular weight diol, there may be used a
polyesterdiol, a polyether diol, a polyether ester diol, a
polycarbonate diol or other high molecular weight diols.
Particularly preferred is a polyester diol obtained by the reaction
of a dihydric alcohol with a divalent carboxylic acid compound, or
a polyester diol obtained by ring-opening polymerization of a
cyclic ester compound. For instance, poly(1,4-butyleneadipate),
poly(ethyleneadipate), poly(1,4-butyleneazelate) or
poly(.epsilon.-caprolactone) may be used. Further, in some cases,
it is preferred to use a polyether diol obtained by adding an
epoxide such as alkylene oxide or other cyclic ether having an at
least 4-membered ring structure to water, a dihydric alcohol, a
dihydric phenol or other initiator, or a polycarbonate diol
obtained by reaction of an aliphatic alicyclic diol with phosgene
or by diester exchange reaction of such diol with a
dialkylcarbonate. These high molecular weight diols are preferably
liquid at a normal temperature or have a low melting point so that
they can be converted to liquid at the time of the reaction. Their
molecular weight is not critical, but is preferably from 600 to
8000, more preferably from 800 to 4000.
The chain extender is a divalent compound having a relatively low
molecular weight, such as a diol, a diamine, a dihydric
alkanolamine or other compounds having two hydroxyl groups or amino
groups. Its molecular weight is not critical, but is preferably not
more than 400, more preferably not more than 200. As the diol,
their may be used a dihydric alcohol, a polyester diol or a
polyether diol. Particularly preferred is a dihydric alcohol having
from 2 to 6 carbon atoms. As the diamine, an aliphatic, alicyclic,
aromatic or other diamine may be used. As the alkanolamine, a
dihydric alkanolamine such as an N-alkyldiethanolamine may be used.
In the combination of the high molecular weight diol with the chain
extender, it is possible to incorporate other divalent compounds
such as diols having a molecular weight inbetween them. Each of the
high molecular weight diol and the chain extender may be a mixture
of two or more respective compounds.
As the diisocyanate compound, there may be used aliphatic,
alicyclic, aromatic or other diisocyanates, or modified compounds
thereof. They may be used alone or in combination as a mixture of
two or more different kinds. An isocyanate group directly bonded to
an aromatic ring is likely to lead to yellowing of the polyurethane
thereby obtained. Therefore, it is preferred to use a diisocyanate
having no such an isocyanate group, i.e. a diisocyanate commonly
called a non-yellowing type. For example, preferred diisocyanates
include hexamethylene diisocyanate, methylene
bis(cyclohexylisocyanate), cyclohexylmethane diisocyanate,
isophorone diisocyanate, xylylene diisocyanate and modified
diisocyanates obtained by modifying these diisocyanates by treating
them with various compounds.
The polyurethane thermoplastic resins may be prepared from the
above-mentioned materials by means of a one-shot method, a
prepolymer method, a modified prepolymer method or various other
methods. By these methods, they may be formed directly into sheets
of films, or they may be formed into sheets or films from
polyurethane solutions or powdery or granular polyurethanes thereby
obtained. For instance, they may be formed into sheets or films by
means of a casting method, an extrusion molding method, an
injection molding method, a pressing method or other methods. In
the case where a multi-layered polyurethane thermoplastic resin, a
laminate of a polyurethane thermoplastic resin with other synthetic
resin, a laminate obtained by laminating the above-mentioned sheets
or films by fusion bonding, press bonding or adhering, or a
laminate prepared by a multi-layer extrusion molding method or
casting method, may be employed.
The exposed surface of the laminated safety glass of the present
invention is prefeably made of a synthetic resin to which
functional groups cross-linkable by light or moisture can readily
be introduced. Namely, in FIG. 1, the entire synthetic resin layer
1 and in each of FIGS. 2 to 4, at least the synthetic resin layer 3
having the exposed surface should preferably made of such a
synthetic resin. In the case of a polyurethane thermoplastic resin
as such a synthetic resin, the polyurethane thermoplastic resin
should preferably have carboxylic acid groups, partially amino
groups or other highly reactive groups. Even without such groups,
it is possible to utilize active groups such as urethane groups
which the resin contains in itself. However, since the functional
groups cross-linkable by light or moisture can readily be
introduced, it is preferred that such highly reactive groups should
be introduced during the preparation of the polyurethane. In the
case of carboxylic acid groups as the highly reactive groups, it is
possible to prepare a polyurethane containing carboxylic acid
groups by using main materials containing carboxylic acid groups
such as a high molecular weight diol containing carboxylic acid
groups and a chain extender having carboxylic acid groups, or a
subsidiary material such as a cross-linking agent having carboxylic
acid groups. These compounds having carboxylic acid groups may be
substituted entirely for the above-mentioned high molecular weight
diol or the chain extender, but is usually employed in combination
therewith. For instance, a carboxylic acid having a hydroxyl group
such as dimethylol propionic acid useful as the chain extender
having a carboxylic acid group is preferably used in combination
with a dihydric alcohol as a common chain extender. Further, in the
case where the carboxylic acid groups are likely to adversely
affect the reaction for the preparation of polyurethane or they are
likely to undergo reaction, it is possible to employ a method
wherein a compound having a group convertible to a carboxylic acid
group is used for the preparation of the polyurethane, and
subsequently that group is converted to a carboxylic acid
group.
The laminated safety glass is prepared by laminating preferably a
thermoplastic resin such as a polyurethane thermoplastic resin with
a hard substrate such as a glass sheet by means of heat-press
bonding, fusion bonding, adhering or other methods. In the case
where the laminated safety glass has a multi-layered structure
having at least three layers, the respective layers may
simultaneously or successively be laminated. Especially when two or
more synthetic resin layers are to be provided, it is preferred to
use their laminate which has been preliminarily prepared. Various
methods for lamination may be employed for the lamination to
prepare a laminate of synthetic resins or a multilayered hard
substrate. For the lamination of a thermoplastic resin with a hard
substrate, heat-press bonding is most suitable. The lamination of
the synthetic resin with the hard substrate usually constitute the
final lamination step in the process for the preparation of
laminated safety glass. However, it is possible to apply further
lamination to prepare laminated safety glass having a layered
structure having three or more layers. For instance, onto the upper
surface of the two layered laminated safety glass as shown in FIG.
1, a further thermoplastic resin sheet or film may be laminated to
obtain a three layered laminated safety glass as shown in FIG.
2.
The heat-press bonding in the above-mentioned lamination is usually
conducted by a combination of a preliminarily press bonding step
wherein a thermoplastic resin and a hard substrate (hereinafter
referred to as a "laminated assembly") is deaerated under reduced
pressure at a normal temperature or under heating to a temperature
not higher than 100.degree. C. to remove e.g. an air present
between the resin and the substrate, and a main press bonding step
wherein the laminated assembly is subjected to heat-press bonding
under heat and pressure. More specifically, the heat-bonding is
carried out, for instance, by placing one or more thermoplastic
resin sheets or films on a hard substrate, placing thereon a mold
material having a smooth surface such as a glass sheet, a rubber
sheet, a plastic sheet or a metal sheet treated with a releasing
agent, putting the laminated assembly thus obtained, in a
preliminary press-bonding envelope made of rubber, deaerating the
press bonding envelope to carry out the preliminary bonding, then
putting the preliminarily press-bonded laminate into a autoclave
after removing or without removing the mold material and applying
pressure and heating to carry out the main press-bonding. The
preliminary press-bonding is usually carried out by reducing the
pressure in the preliminarily press-bonding envelope to a level of
at most about 700 mmHg, e.g. from 200 to 650 mmHg, and then heating
to a temperature of a level of at most about 100.degree. C., e.g.
from a normal temperature to 90.degree. C. Whereas, the main
press-bonding is preferably conducted usually at a temperature of
from about 60.degree. C. to a melting point of the thermoplastic
resin, e.g. from about 80.degree. to about 150.degree. C. in the
case where the thermoplastic resin is a polyurethane thermoplastic
resin, under pressure of at least 2 kg/cm.sup.2, e.g. from about 7
to 20 kg/cm.sup.2 in the case of a polyurethane thermoplastic
resin. These conditions may vary depending upon the types of the
thermoplastic resin or the hard substrate, the thickness of size of
each constituent unit or other factors.
The above-mentioned preliminary press-bonding is not restricted to
the method of using a preliminary press-bonding envelope. For
instance, it may be carried out by a method wherein the laminated
assembly is passed through a pair of rolls to carry out the
preliminary press-bonding by roll pressure, a method wherein the
laminated assembly is pressed by a platen to carry out the
preliminary press-bonding, or a double vacuum press-bonding method
wherein the laminated assembly is placed in an inner reduced
pressure chamber of a reduced pressure apparatus having double
reduced pressure chambers, the outer reduced pressure chamber is
firstly deaerated and then the inner reduced chamber is deaerated,
and then the reduced pressure of the outer reduced pressure chamber
is released, whereby press-bonding is carried out under atmospheric
pressure. Likewise, the main press-bonding is not limited to the
method of heat press-bonding by means of an autoclave, and may be
conducted, for instance, by a method wherein the laminated assembly
is pressed in a heated oil bath, a method wherein the laminated
assembly is passed through a pair of rolls for pressing under
heating, a method wherein the laminated assembly is pressed under
heating or a method wherein the above-mentioned double vacuum
press-bonding is carried out under heating. Further, in the heat
press-bonding, particularly in the preliminary press-bonding step,
it is preferred to use the above-mentioned mold material which is
placed on the thermoplastic resin to ensure adequate press-bonding
and to obtain a smooth surface and which is removed after the
press-bonding. However, depending upon the purpose or the type of
the press-bonding method, the use of such a mold method may be
omitted. Further, the heat press-bonding of the thermoplastic resin
with the hard substrate is conducted most commonly by way of the
preliminary press-bonding step and the main press-bonding step.
However, depending upon the conditions including the type of the
heat press-bonding method, the type of the thermoplastic resin or
the hard substrate, or the thickness or size of each constituent
unit, the heat press-bonding can be conducted in a single step
without necessity to cary out both steps of the preliminary
press-bonding step and the main press-bonding step.
The lamination of the above-mentioned heat press-bonding is not
only the process for the preparation of the laminated safety glass.
However, such heat press-bonding has various advantages over other
methods, such that a higher bonding strength between the
thermoplastic resin and the hard substrate is obtainable, the
thermoplastic resin can preliminarily formed into a sheet or film,
whereby a smooth thermoplastic resin layer having good optical
properties is obtainable, or the thermoplastic resin layer can be
pressed with a mold material during the heat press-bonding, whereby
a further improved smooth surface is obtainable. The laminated
safety glass is preferably composed of a hard substrate and a
thermoplastic resin layer having a single or multi-layered
structure and contains no thermosetting resin layer between the
hard substrate and the thermoplastic resin layer or between the
layers of thermoplastic resin. However, in some cases, it may have
a thin layer of a adhesive, a binder or other thermosetting resins.
However, it does not have a thermoplastic resin layer at the
exposed surface of the synthetic resin layer, as opposed to the
case of the aforementioned prior art reference. Further, in the
case where the hard substrate facing the synthetic resin layer is
glass (inorganic glass), it is preferred that there is no
thermosetting resin layer between the resin layer and the glass
substrate.
The introduction of the above-mentioned cross-linkable groups and
the subsequent cross-linking of the cross-linkable groups may be
conducted at an optional stage during the process for the
preparation of the laminated safety glass. For instance, at an
early stage, it is possible to introduce and cross-link the
cross-linkable groups in a surface which will eventually constitute
the exposed surface of the laminated safety glass and then use such
material for the preparation of the laminated safety glass of the
present invention. At a later stage, it is possible to introduce
and cross-link the cross-linkable groups to the exposed surface of
the synthetic resin layer after the fabrication of laminated safety
glass. The introduction and cross-linking of the cross-linkable
groups are not necessarily conducted consecutively, and it is
possible to interpose various steps between the two operations. For
instance, it is possible to firstly introduce the cross-linkable
groups into one side of a thermoplastic resin sheet or film, then
to use it or to combine it with other synthetic resin for the
lamination with a hard substrate by e.g. heat press-bonding to
prepare laminated safety glass, and then to cross-link the
cross-linkable groups present in the surface of the synthetic resin
layer to obtain laminated safety glass of the present invention.
More specifically, for instance, the above-mentioned compound
having an epoxy group and an alkoxysilyl group, such as
.gamma.-glycidoxypropyltrimethoxysilane, is coated, by itself or in
a form of a solution, on a carboxylic acid group-containing surface
of the above-mentioned polyurethane thermoplastic resin sheet or
film having carboxylic acid groups, on a synthetic resin laminate
having such a sheet or film on its surface or on laminated safety
glass having such layers, and it is reacted to introduce the
alkoxysilyl group into the surface. Then, this alkoxysilyl group is
cross-linked. In the case of the synthetic resin sheet or film,
this cross-linking may be conducted after laminating it with a hard
substrate. As mentioned above, the cross-linking of the alkoxysilyl
group is carried out by hydrolysis of the alkoxysilyl group and
dehydration condensation of the resulting silanol group. This two
step reaction can be conducted separately. For instance, it is
possible that a sheet or film of a synthetic resin having silanol
groups formed by the hydrolysis of the alkoxysilyl groups, is
laminated on a hard substrate and then the laminate is subjected to
the dehydration condensation of the silanol groups. Likewise, it is
possible that e.g. a compound having an epoxy group and a
light-cross-linkable group (for instance, a cinnamic acid group) is
reacted to the surface of a polyurethane thermoplastic resin having
carboxylic acid groups, and light such as ultra-violet ray is
irradiated to this light-cross-linkable group to obtain a surface
having a cross-linked structure. Further, heat cross-linking may be
conducted by a method wherein a compound having an isocyanate group
or groups having active hydrogen are reacted under heating to a
sheet or film of a thermoplastic polyurethane having hydroxyl
groups, amino groups, urethane groups, or other groups having
active hydrogen or isocyanate groups to carry out the
cross-linking, or a method wherein a cross-linking agent such as a
peroxide is used. In some cases, this heat cross-linking is
preferably carried out simultaneously during the lamination of the
thermoplastic polyurethane with a glass sheet.
Specific preferred processes for the production of the laminated
safety glass of the present invention are generally classified into
three methods.
In the first method, a thermoplastic resin sheet or film having a
preliminarily formed cross-linked structure on one side and a hard
substrate are bonded by heat-pressing so that the surface of the
sheet or film having no cross-linked structure constitutes the
bonding surface. In this case, the lamination may be made by
interposing a second thermoplastic resin sheet or film between the
above-mentioned sheet or film and the hard substrate. For instance,
laminated safety glass may be obtained by firstly introducing
cross-linkable groups into one surface of a sheet or film of a
polyurethane thermoplastic resin having carboxylic acid groups,
then cross-linking the cross-linkable groups to obtain a
polyurethane thermoplastic resin sheet or film having a
cross-linked structure on one surface and no cross-linked structure
on the other surface, and bonding by heat-pressing a glass sheet to
the other surface of the polyurethane thermoplastic resin sheet or
film. Instead of a single layered polyurethane thermoplastic resin
sheet or film, a laminate of such a sheet or film with a sheet or
film of further polyurethane thermoplastic resin having no
carboxylic acid groups may be used. In such a case, the
introduction and cross-linking of the cross-linkable groups in the
surface containing carboxylic acid groups may be carried out prior
to or after the lamination. FIGS. 5 to 8 is a schematic view
illustrating this method. A thermoplastic resin sheet or film 8
having a cross-linked structure on one surface C and no
cross-linked structure on the other surface D is placed between a
mold material 6 and a hard substrate 7, and heat press-bonding is
carried out to obtain laminated safety glass. FIG. 5 illutrates a
case wherein a single layered thermoplastic resin sheet or film 8
is used, FIG. 6 illustrates a case wherein a two layered
thermoplastic resin sheet or film 8 is used. And FIG. 7 illustrates
a case wherein a second thermoplastic resin sheet or film 8 is
interposed between the thermoplastic resin sheet or film 8 and the
hard substrate 7. FIG. 8 illustrates a case wherein a laminated
glass sheet having an intermediate film is used as the hard
substrate.
In the second method, cross-linkable groups are introduced into one
surface of a thermoplastic resin sheet or film, a hard substrate is
bonded to the other surface of the sheet or film, and thereafter
the cross-linkable groups are cross-linked. In some cases, the
cross-linking of the cross-linkable groups may be conducted
simultaneously with the heat press-bonding. The heat press-bonding
may be conducted in the same manner as in the first method except
that the heat press-bonding is carried out without preliminary
cross-linking the cross-linkable groups. For instance, referring to
FIGS. 5 to 8, the heat press-bonding is carried out by using a
thermoplastic resin sheet or film having a surface containing
cross-linkable groups instead of the surface C having a
cross-linked structure, and the cross-linking of the cross-linkable
groups is conducted after the heat press-bonding or at the same
time as the heat press-bonding, to obtain laminated safety
glass.
In the third method, after the preparation of laminated safety
glass having a thermoplastic resin layer on one side, i.e.
resin-laminated glass, cross-linkable groups are introduced in the
exposed surface of the thermoplastic resin layer and then the
cross-linkable groups are cross-linked. The preparation of the
resin-laminated glass is preferably carried out by the
above-mentioned heat press-bonding. Further, the thermoplastic
resin constituting the exposed surface is preferably made of a
polyurethane thermoplastic resin having carboxylic acid groups.
The transparent or translucent laminated safety glass obtained by
the present invention is suitable for use as a window material for
an automobile or other vehicle, or as window material for
buildings. However, its use is not restricted to these specific
examples, it may be used for various other applications where
transparency and physical strength are required, for instance, for
eye glasses.
Now, the present invention will be described in further detail with
reference to a Reference Example and Examples. However, it should
be understood that the present invention is by no means restricted
to these specific Examples.
REFERENCE EXAMPLE
Polyurethane sheets were prepared in accordance with the following
methods. The sheets thereby obtained are designated as Sheets A to
E, and they were used in the subsequent Examples.
Sheet A
1500 g of polybutyleneadipate having a hydroxyl group value of 56
was dehydrated under vacuum of 3 mmHg at 110.degree. C. for 2
hours. Added thereto are 908 g of isophorone diisocynate
(3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate) and 0.16
g of di-n-butyltin dilaurate, and the mixture was reacted at
80.degree. C. for 15 minutes under nitrogen stream. Then, 244 g of
1,4-butanediol and 75 g of dimethylol propionic acid were added to
this reaction mixture, and the mixture was immediately stirred and
mixed. As the reaction started, heat was generated, whereby a
substantially uniform mixture was obtained. This liquid reaction
mixture was poured into a vat coated with Teflon and reacted at
110.degree. C. for 12 hours. The polymer thereby formed was
pulverized by a pulverizer to obtain a granular product, which is
then formed into a thermoplastic polyurethane sheet having a
thickness of 0.6 mm by an extruder. This sheet was designated as
Sheet A.
Sheet B
Sheet B having a thickness of 0.6 mm was prepared in the same
manner as in the case of Sheet A by using 1500 g of polyethylene
adipate having a hydroxyl group value of 56.7, 781 g of
4,4'-methylene-bis(cyclohexyl isocyanate), 0.45 g of di-n-butyltin
dilaurate, 144 g of 1,4-butanediol and 75 g of dimethylolpropionic
acid.
Sheet C
Sheet C having a thickness of 0.6 mm was prepared in the same
manner as in the case of Sheet A by using 1500 g of polybutylene
adipate having a hydroxyl group value of 54.3, 642 g of
4,4'-methylene-bis(cyclohexyl isocyanate), 0.33 g of di-n-butyltin
dilaurate, 121 g of 1,4-butanediol and 45 g of dimethylolpropionic
acid.
Sheet D
Sheet D having a thickness of 0.6 mm was prepared in the same
manner as in the case of Sheet A by using 1500 g of polyethylene
adipate having a hydroxyl group value of 56, 1173 g of
4,4'-methylene-bis(cyclohexyl isocyanate), 327 g of 1,4-butanediol
and 0.18 g of di-n-butyltin dilaurate.
Sheet E
Sheet E having a thickness of 0.6 mm was prepared in the same
manner as in the case of Sheet A by using 1500 g of
polycaprolactonediol having a hydroxyl group value of 55.8, 1003 g
of 4,4'-methylene-bis(cyclohexyl isocyanate), 0.33 g of
di-n-butyltin dilaurate, 150 g of 1,4-butanediol and 75 g of
dimethylol propionic acid.
EXAMPLE 1
A solution containing 50 g of glycidylcinnamate, 15 g of
polyethyltriethylamine, 5 g of 2,2-dimethoxy-2-phenylacetophenone
and 500 g of benzene, was uniformly coated on one surface of Sheet
A, and reacted for 1 hour in a furnace purged with nitrogen and
kept at 110.degree. C. Then, light from a 100 W high pressure
mercury lamp was irradiated to the surface treated with
glycidylcinnamate, for 5 minutes from a distance of 5 cm.
Thereafter, Sheet A was sandwiched between a pair of glass sheets.
At that time, the surface of one of the glass sheets which was
brought in contact with the light-treated surface of the Sheet A
was preliminarily uniformly coated with polydimethyl siloxane and
subjected to heat treatment at 350.degree. C. This non-bonded glass
laminate was put in a rubber envelope and the rubber envelope
containing the laminate was placed in an autoclave. Firstly, both
of the rubber envelope and the autoclave were vacuumed to remove an
air between the glass sheets and Sheet A. Then, the autoclave was
heated to 100.degree. C., and while maintaining the vacuumed state
in the rubber envelope, the pressure in the autoclave was returned
to atmospheric pressure, whereby pressure of 1 kg/cm.sup.2 was
exerted. This condition was maintained for 15 minutes, and then
autoclave was set at a temperature of 140.degree. C. under pressure
of 13 kg/cm.sup.2 and maintained under these conditions for 20
minutes. The glass laminate was withdrawn from the autoclave, and
then the glass sheet treated with polydimethylcycloxane was
removed, whereby resin-laminated glass with the exposed surface of
Sheet A being smooth like a glass surface and having good adhesion
between the glass sheet and Sheet A was obtained.
The surface of Sheet A of this resin-laminated glass was subjected
to a rubbing test with a felt cloth impregnated with each of
ethanol/methanol=10/1 (V/V), carbon tetrachloride, kerosine and
gasoline. No change was observed after rubbing the surface 1000
times. Further, in a Taber's abrasion resistance test according to
JIS R-3212, an increase of the haze after the abrasion of 100 times
was 2.5%. In a falling ball impact test according to the same JIS
R-3212, the steel ball did not penetrate, thus indicating adequate
penetration resistance.
Hereinafter, the above-mentioned testing methods are referred to as
a rubbing test, a Taber's test and a falling ball test,
respectively, and the results of the respective tests in each
Example will be shown.
EXAMPLE 2
A solution comprising 50 g of glycidyl methacrylate, 15 g of
N,N'-dimethylaniline, 5 g of benzoinmethylether and 500 g of
benzene, was uniformly coated on one surface of Sheet B, and
reacted for 30 minutes in a furnace purged with nitrogen and kept
at 110.degree. C. Then, in the same manner as in Example 1,
irradiation was carried out, and then the Sheet B was laminated
with a glass sheet to obtain resin-laminated glass.
This resin-laminated glass was subjected to the tests, and the
results thereby obtained were as follows:
______________________________________ Rubbing test No change
Taber's test Haze increase of 2.3% Falling ball test No penetration
______________________________________
EXAMPLE 3
A mixture of .gamma.-glycidoxy propyltrimethoxysilane and a trace
amount of N,N-dimethylaniline was extremely thinly and uniformly
coated on one side of Sheet C, and reacted at a temperature of
110.degree. C. for 30 minutes in a furnace purged with nitrogen.
This Sheet C was immersed for 30 minutes in hot water of 90.degree.
C., and then dried in a drier at 120.degree. C. for 15 minutes.
Thereafter, in the same manner as in Example 1, resin-laminated
glass was prepared. The surface of Sheet C of this resin-laminated
glass was smooth like a glass surface and had no optical
distortion. Further, the adhesion of Sheet C with glass was
excellent.
______________________________________ Rubbing test No change
Taber's test Haze increase of 2.0% Falling ball test No penetration
______________________________________
EXAMPLE 4
A solution comprising 50 g of .gamma.-isocyanate propyltrimethoxy
silane, 0.5 g of lead octylate and 500 g of benzene was uniformly
coated on one surface of Sheet D, and reacted at a temperature of
110.degree. C. for 1 hour in a furnace purged with nitrogen. With
this sheet, resin-laminated glass was prepared in the same manner
as in Example 3.
______________________________________ Rubbing test No change
Taber's test Haze increase of 2.4% Falling ball test No penetration
______________________________________
EXAMPLE 5
In Example 1, Sheet A treated on one surface with glycidyl
cinnamate was laminated with a glass sheet in the same manner as in
Example 1 without irradiation, whereby resin-laminated glass having
a polyurethane sheet layer with its surface non-cross-linked. This
polyurethane sheet layer was smooth like a glass surface and its
adhesion with the glass sheet was excellent.
Then, light from a 100 W high pressure mercury lamp was irradiated
to the surface of Sheet A of this resin-laminated glass from a
distance of 5 cm for 5 minutes. The physical properties of the
surface of the Sheet A thus cross-linked by irradiation and the
penetration resistance of this resin-laminated glass were as
follows.
______________________________________ Rubbing test No change
Taber's test Haze increase of 2.6% Falling ball test No penetration
______________________________________
EXAMPLE 6
Sheet B prepared in Example 2 and having non-cross-linked
light-cross-linkable groups on one surface was laminated in the
same manner as in Example 1 without irradiation, whereby
resin-laminated glass was prepared. Then, irradiation was carried
out in the same manner as in Example 5, whereby resin-laminated
glass having a cross-linked surface was obtained.
______________________________________ Rubbing test No change
Taber's test Haze increase of 2.3% Falling ball test No penetration
______________________________________
EXAMPLE 7
A mixture of .gamma.-glycidoxy propyltrimethoxysilane and a trace
amount of N,N-dimethylaniline was thinly and uniformly coated on
one surface of Sheet C, and subjected to heat treatment at
110.degree. C. for 30 minutes in a furnace purged with nitrogen.
This surface-treated Sheet C was laminated with a glass sheet in
the same manner as in Example 1 to obtain resin-laminated
glass.
Then, this resin-laminated glass was immersed for 30 minutes in hot
water of 90.degree. C., and then dried in a drier at 120.degree. C.
for 15 minutes. The film surface of this resin-laminated glass was
smooth, and the adhesion of the film with the glass sheet was
excellent.
______________________________________ Rubbing test No change
Taber's test Haze increase of 2.0% Falling ball test No penetration
______________________________________
EXAMPLE 8
Resin-laminated glass was prepared in the same manner as in Example
7 except that instead of .gamma.-glycidoxy propyltrimethoxysilane
in Example 7, .beta.-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was
used.Thereafter, hot water treatment and drying were carried out in
the same manner, whereby satisfactory resin-laminated glass was
obtained.
______________________________________ Rubbing test No change
Taber's test Haze increase of 2.6% Falling ball test No penetration
______________________________________
EXAMPLE 9
Resin-laminated glass having the thermoplastic polyurethane layer
having a moisture-cross-linked surface was prepared in the same
manner as Example 7 except that Sheet E was used.
______________________________________ Rubbing test No change
Taber's test Haze increase of 2.9% Falling ball test No penetration
______________________________________
EXAMPLE 10
Resin-laminated glass was prepared in accordance with the
lamination method of Example 1 without applying surface treatment
to Sheet A. (Resin-laminated glass prepared by laminating a sheet
with no surface treatment and glass will be hereinafter referred to
as "non-treated resin-laminated glass".) The thermoplastic
polyurethane layer of this resin-laminated glass was firmly bonded
to the glass sheet, and its exposed surface was smooth.
Then, a solution comprising 50 g of .gamma.-glycidoxy
propyltrimethoxysilane, 0.5 g of N,N'-dimethylaniline and 500 g of
n-hexane was uniformly coated on the exposed surface of the
polyurethane sheet of this non-treated resin-laminated glass, and
reacted at a temperature of 110.degree. C. for 30 minutes in a
nitrogen atmosphere. Thereafter, the resin-laminated glass was
immersed in hot water at 90.degree. C. for 30 minutes, and then
dried in a drier at 126.degree. C. for 20 minutes. The polyurethane
sheet surface of this resin-laminated glass was smooth like a glass
surface, and the resin-laminated glass was also optically
excellent.
______________________________________ Rubbing test No change
Taber's test Haze increase of 2.5% Falling ball test No penetration
______________________________________
The above-mentioned non-treated resin-laminated glass was subjected
to a rubbing test, whereby the surface was impaired when subjected
to rubbing with an ethanol/methanol mixed solution, and its haze
increase was 30%.
EXAMPLE 11
With use of Sheet E, non-treated resin-laminated glass was prepared
in the same manner as in Example 10. Then, it was treated in the
same manner as in Example 1, whereby surface-treated excellent
resin-laminated glass was obtained.
______________________________________ Rubbing test No change
Taber's test Haze increase of 2.9% Falling ball test No penetration
______________________________________
EXAMPLE 12
A solution comprising 50 g of glycidyl methacrylate, 0.5 g of
N,N'-dimethylaniline, 5 g of benzoinmethylether and 500 g of
benzene was uniformly coated on the polyurethane sheet surface of
the non-treated resin-laminated glass of Example 10, and reacted at
a temperature of 110.degree. C. for 30 minutes in a nitrogen
atmosphere. Thereafter, light from a 100 W high pressure mercury
lamp was irradiated to the polyurethane sheet surface of this
resin-laminated glass for 10 minutes, whereby surface treated
excellent resin-laminated glass was obtained.
______________________________________ Rubbing test No change
Taber's test Haze increase of 2.6% Falling ball test No penetration
______________________________________
EXAMPLE 13
With use of Sheet D, non-treated resin-laminated glass was
prepared. A solution comprising 50 g of .gamma.-isocyanate
propyltrimethoxy-silane, 0.5 g of octylic acid and 500 g of benzene
was uniformly coated on the polyurethane sheet surface of this
non-treated resin-laminated glass, and reacted at a temperature of
110.degree. C. for 1 hour in a nitrogen atmosphere. Thereafter, it
was immersed in hot water at 90.degree. C. for 30 minutes and then
dried at 120.degree. C. for 20 minutes, whereby surface-treated
excellent resin-laminated glass was obtained.
______________________________________ Rubbing test No change
Taber's test Haze increase of 2.4% Falling ball test No penetration
______________________________________
EXAMPLE 14
Surface-treated excellent resin-laminated glass was obtained in the
same manner as in Example 12 except that instead of glycidyl
methacrylate, glycidylcinnamate was used.
______________________________________ Rubbing test No change
Taber's test Haze increase of 2.8% Falling ball test No penetration
______________________________________
EXAMPLE 15
A sheet having a thickness of 0.6 mm was prepared in the same
manner as in the case of Sheet A except that 1500 g of
poly(butyleneadipate) having a hydroxyl group value of 54.1, 148 g
of 1,4-butane diol, 75 g of dimethylol propionic acid and 0.45 g of
di-n-butyltindilaurate were used.
Then, with use of this sheet, resin-laminated glass was prepared by
the same lamination method as in Example 1. In this case, however,
a solution comprising 50 g of 1,4-butane diol, 0.5 g of
N,N'-dimethylaniline and 100 g of tetrahydrofuran was uniformly
coated on the sheet surface treated with polydimethylsiloxane and
which is in contact with glass, and dried in an air. The surface of
the thermoplastic polyurethane layer of the surface-treated
resin-laminated glass thus obtained was smooth, and the
resin-laminated glass was optically excellent.
______________________________________ Rubbing test No change
Taber's test Haze increase of 2.4% Falling ball test No penetration
______________________________________
EXAMPLE 16
Excellent resin-laminated glass was prepared in the same manner as
in Example 15 except that 1500 g of polybutylene adipate having a
hydroxyl group value of 54.1, 798 g of
4,4'-methylenebis(cyclohexylisocyanate), 127 g of 1,4-butane diol,
75 g of cis-1,4-butene-2-diol and 0.15 g of di-n-butyltindilaurate
were used and 2,5-dimethyl-2,5-di-t-butylperoxyhexane was uniformly
coated as a treating agent to the sheet surface.
______________________________________ Rubbing test No change
Taber's test Haze increase of 2.5% Falling ball test No penetration
______________________________________
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